Nonylphenol ethoxylates (NPEs) in textile products, and their

Greenpeace Research Laboratories Technical Report 01/2012 3

Washing of articles

The effect of washing under simulated standard domestic laundering conditions was also investigated for some of the textile products in which NPEs were identified. This aspect was investigated for 14 samples, consisting of 12 samples of plain fabric (with concentrations in the unwashed fabric ranging from 11 mg/kg to 1100 mg/kg), and 2 samples of fabric bearing a plastisol print (with unwashed fabric concentrations of 470 mg/kg and 27000 mg/kg respectively).

Key findings

• For all samples, the concentration of NPEs in the washed fabric was lower than that in an unwashed portion of identical fabric from the same item following a single wash; washed fabric concentrations of NPEs were between 6% and 83% of the concentrations in the unwashed portions of the plain fabrics, and were 44% and 91% of the unwashed fabric concentrations for the two plastisol-printed samples.

• The results equate to between 17% and 94% of NPE residues being washed out from the plain fabric samples during a single wash, and between 9% and 56% from plastisol-printed samples, assuming that the unwashed and washed portions from each item initially contained the same concentration of NPEs.

• For half the plain fabric samples (6 of 12), concentrations of NPEs in the washed portion were below 20% of those determined in the unwashed portions of the same fabric.

• The apparent reductions in NPE concentrations due to washing were largely independent of the initial concentrations in the unwashed products. In other words, the fabrics yielding the greatest difference between NPE concentrations in washed and unwashed portions were not necessarily those with the highest NPE concentrations in the unwashed portions.

• The type of fabric that a product is made from does not appear to influence the extent to which concentrations are lower in the washed portion compared to the unwashed portion.

These results indicate that a single wash, using conditions intended to simulate standard domestic laundering, can wash out a substantial fraction of NPE residues present within textile products, with more than 80% being washed out for half the plain fabric samples.

As far as we are aware, this is the first study to report differences in the amounts of NPEs in fabric products before and after washing using simulated domestic laundering conditions. Given that NPEs are readily water soluble, it is not surprising that residues are washed out from fabrics to this extent, even after a single wash.

The release of NPEs from the washing of clothes and other fabric products contributes to ongoing inputs of nonylphenol to surface waters, predominantly via urban wastewater and sewage treatment plants. Although the contribution of NPEs from any given article of clothing will be relatively small, the sheer volume of clothing being sold and subsequently washed means that the total quantities being released may be substantial. Within the EU, where the use of nonylphenol and NPEs in clothing manufacture has effectively been banned, releases due to the washing of such products has been estimated to constitute by far the largest source of these chemicals entering waste water treatment facilities in some instances. Despite requirements made in 2000 under the Water Framework Directive (WFD) that all releases of nonylphenol within the EU are phased out within 20 years, inputs to surface waters continue within the EU via this route.

Until restrictions on the import of textile products containing residues of NPEs into the EU are in place, alongside product brands completely eliminating all uses of NPEs in their supply chains, releases of NPEs from textiles and the resulting inputs of nonylphenol to surface waters will continue to contribute to overall releases within the EU.

Similarly, release of these substances will continue in countries outside the EU where few or no effective controls on their manufacture, use and release are currently in place, both from the manufacture of products and their subsequent washing.


Introduction

Nonylphenol ethoxylates (NPEs) are a group of chemicals used as surfactants, emulsifiers, dispersants and wetting agents in a variety of applications, including the manufacture of textiles. Where released, either directly into surface waters or via wastewater treatment facilities, NPEs can break down to form nonylphenols, a closely-related group of persistent, bioaccumulative and toxic chemicals (OSPAR 2004 Jobling et al. 1996). The manufacture, use and release of nonylphenol and NPE are regulated in some regions (OSPAR 1998, EU 2003), though uses continue elsewhere. Additional information on nonylphenol and NPEs, including on their hazardous properties, is available in a previous related report (Greenpeace 2011a).

The use of NPEs during the manufacture of textiles can leave residues of NPEs within the final product. Some previous studies have reported the presence of NPEs within textile products, though these studies have tended to focus on a relatively small number of products sold within a single country (Laursen et al. 2003, Greenpeace 2004, LGC 2006, Månsson et al. 2008, SSNC 2008).

This study was carried out to provide a more comprehensive and up-to-date understanding of the presence and levels of NPEs within textile products across a wide range of countries of manufacture and sale, and for a wide range of major clothing brands (Part 1). In addition, this study investigated the potential for NPEs (which are water-soluble) to be washed out from products under conditions intended to simulate standard domestic laundering (Part 2).

Part 1 – Quantification of NPEs in textile products

The concentrations of NPEs were quantified in articles of clothing and fabric-based shoes. This study involved the analysis of 78 articles (including sports and recreational clothing and shoes) bearing the logos of 15 leading clothing brands. These products were purchased in 18 countries, including 10 within the EU. According to their labels, the products were manufactured in at least 13 different countries, with three items being of unknown manufacturing origin. The products included those manufactured from natural and from synthetic fabrics, and included items designed for men, women and children. The study covered a variety of items, including shirts, jackets, trousers, underwear and fabric based shoes.

For the majority of products (71 of 78), a section of plain fabric from the item was tested. For the remaining 7 products, the concentration of NPEs was quantified in a section of fabric bearing a plastisol print of an image, logo or text.

The results from this section have also been reported in ‘Dirty Laundry 2: Hung Out to Dry’ (Greenpeace 2011b).

Methodology

The 78 products were purchased during April and May 2011 at the flagship stores of the clothing brands, or other stores authorised to sell the branded products, in 18 countries (see Appendix 1 for details). While still in the store, purchased products were immediately sealed in individual clean polyethylene bags.

Sealed bags containing the products were sent to the Greenpeace Research Laboratories at the University of Exeter in the UK, from where they were dispatched to an independent accredited laboratory for analysis.

Quantification of nonylphenol ethoxylates

For 71 of the 78 products, a section of fabric that did not bear any printing was removed from the product for subsequent analysis. For the remaining 7 products, a section bearing a plastisol print of an image, logo or text on the surface was removed from the product for analysis.

Following isolation of a section of fabric, the sample was extracted with an acetonitrile-water mixture in the ratio 70:30 and then analysed with reversed-phase HPLC liquid chromatography along with Applied Biosystems’ API 4000 tandem mass spectrometry (LC-MS/MS). The quantification was carried out for each of 17 individual nonylphenol ethoxylates, consisting of those with 4 to 20 ethoxylate groups. The quantitative results presented below are the sum of the concentrations of the individual nonylphenol ethoxylates with 4-20 ethoxylate groups.

Quality assurance and quality control checks were employed, including the analysis of blank samples, the analysis of a number of samples in duplicate, and the analysis of two intra-laboratory textile reference samples with every batch.

Results and discussion

Of the 78 articles analysed, 52 (two-thirds) tested positive for the presence of NPEs at concentrations above the limit of detection (1 mg/kg). Where detected, levels of NPEs in plain fabric samples ranged from just above 1 mg/kg to 1100 mg/kg. Levels in samples bearing a plastisol print ranged from 5.0 mg/kg up to 27 000 mg/kg, the latter being the highest concentrations among all samples.


Just under one fifth (18%) of the samples contained NPEs at concentrations above 100 mg/kg and, of these, two samples had concentrations over 1000 mg/kg (0.1%). The remainder, almost a half (49%) of all samples tested, contained NPEs at concentrations below 100 mg/kg. A summary of the number of samples containing NPEs within various ranges of concentration is given in Table 1.

Products from 12 of the 13 countries of manufacture contained NPEs above the detection limit (the exception being one sample from Tunisia). Furthermore, NPEs were detected in products from 14 of the 15 product brands (the exception being two samples from GAP), and in products purchased in 17 out of the 18 countries (the exception being two samples from Sweden). A summary of the results is presented in Tables 2 to 4, which include a breakdown of the results by country of purchase, by country of manufacture, and by brand, respectively. The results for individual samples are presented in Appendix 1.

Table 1. The number of samples (of the 78 items tested) within various NPE concentration ranges.

NPE concentration range (mg/kg) Number of samples (of 78 analysed)

<1 26 samples (33%) 1 – 10 17 samples (22%)

10 – 100 21 samples (27%) 100 – 1000 12 samples (15%)

>1000 2 samples (3%)

Samples with higher NPE concentrations (above 100 mg/kg) were distributed across a range of countries of purchase, countries of manufacture and product brands. Given the wide range of NPE concentrations found among individual samples and the relatively small number of products we were able to analyse for any given category (compared to the vast number of products manufactured and sold per country or per brand), it is not possible to draw more general conclusions on the variability of NPE concentrations between product types, country of purchase or manufacture, product brand or fabric type.

Table 2. The number of samples in which NPEs were identified by country of purchase, with the NPE concentration range and the median NPE concentration for each country (* denotes EU member states).

Country of Purchase Number of samples Number tested positive

NPE concentration range (mg/kg)

NPE concentration median (mg/kg)

Argentina 4 4 1.2 - 51 16 Austria * 4 2 <1 - 970 6.3 China 10 7 <1 - 530 14 Czech Republic * 4 1 <1 - 1.8 <1 Denmark * 3 2 <1 - 39 35 Finland * 1 1 660 660 Germany * 7 4 <1 - 680 14 Italy * 4 3 <1 - 240 111 Japan 5 3 <1 - 1100 8.7 Netherlands * 5 3 <1 – 21 1.6 Norway 2 2 13 – 14 14 Philippines 4 2 <1 – 27000 3.8 Russia 4 4 4.4 – 810 15 Spain * 4 3 <1 – 41 21 Sweden * 2 0 <1 <1 Switzerland 6 5 <1 – 160 2.2 Thailand 4 4 2.8 – 470 11 UK * 5 2 <1 – 18 <1 Total 78 52 <1 - 27000 6.3


Table 3. The number of samples in which NPEs were identified by country of manufacture, with the NPE concentration range and the median NPE concentration for each country.

Country of manufacture Number of samples

Number tested positive



Bangladesh 11 8 <1 - 970 13 Cambodia 2 2 1.2 – 18 9.6 China 28 19 <1 – 1100 10 Egypt 1 1 9.1 9.1 Indonesia 3 2 <1 – 35 2.0 Malaysia 2 2 2.8 – 12 7.4 Pakistan 1 1 240 240 Philippines 4 3 <1 – 27000 111 Sri Lanka 1 1 160 160 Thailand 6 5 <1 – 470 11 Tunisia 1 0 <1 <1 Turkey 9 5 <1 – 47 1.6 Vietnam 6 3 <1 - 140 7.3 Unknown 3 0 <1 <1

Table 4. The number of samples in which NPEs were identified by product brand, with the NPE concentration range and the median NPE concentration for each brand.

Brand Number of samples Number tested positive



Abercrombie & Fitch 3 3 18 – 1100 39

Adidas 9 4 <1 - 18 <1

Calvin Klein 4 3 <1 - 160 19

Converse 6 5 <1 - 27000 24

G-Star Raw 5 3 <1 – 41 11

GAP 2 0 <1 <1

H&M 6 4 <1 - 21 4.1

Kappa 5 4 <1 - 970 240

Lacoste 4 1 <1 - 3.6 <1

Li Ning 4 4 2.8 – 680 8.5

Nike 10 5 <1 – 810 <1

Puma 9 7 <1 – 210 4.4

Ralph Lauren 4 3 <1 – 220 43

Uniqlo 4 3 <1 – 25 5.5

Youngor 3 3 19 – 530 190

A summary of the NPE concentrations for different types of fabric is given in Table 5. There are some notable differences between the median concentrations for different fabrics and between the upper values of the concentration ranges for different fabrics, though variability within each fabric type was high and no clear pattern emerges. Due to the small number of samples available from most types of fabric, it is not possible to draw any more generic conclusions on the variability of NPE concentrations between different fabric types.

Table 5. The number of samples in which NPEs were identified by fabric type, with the NPE concentration range and the median NPE concentration for each brand.

Fabric Number of samples Number tested positive



Cotton 30 16 <1 – 970 1.4

Polyester 10 7 <1 - 240 9.6

Cotton, elastane 5 4 <1 – 1100 11

Cotton, polyester 4 4 1.8 – 810 355

Polyester, elastane 3 2 <1 – 2.8 1.2

Cotton, polyester, elastane 2 2 2.0 – 8.7 5.4

Nylon, elastane 1 1 9.1 9.1

Plastisol print 7 4 <1 – 27000 5.0

Unknown 16 12 1.1 – 680 18


Part 2. Analysis of selected samples following washing

NPEs are readily water-soluble and residues in fabrics are, therefore, susceptible to loss to the water phase during laundering under standard domestic conditions. For this reason, a number of the textile products in which NPEs were identified were selected for subsequent investigation into the effect on residue concentrations of washing the product under conditions intended to simulate standard domestic laundering. Fourteen samples were selected, consisting of 12 samples of plain fabric and 2 samples of fabric bearing a plastisol print. The 12 plain fabric samples were selected to provide a broad range of concentrations in the unwashed fabric (from 11 mg/kg to 1100 mg/kg), as well as providing a range of different kinds of products and fabrics.

Similarly, the two samples bearing a plastisol print were selected to provide one material with a high concentration of NPEs in the unwashed fabric (27000 mg/kg) and another with a lower concentration (470 mg/kg). Both plastisol samples were isolated from T-shirts in which the fabric type was not specified.

Details of the individual products, including the concentrations of NPEs in the unwashed fabric, the kind of product and the type of fabric are summarised in Table 6, along with the concentrations of NPEs determined in the fabrics following a single wash.

Methodology

Each product was washed separately according to the standard method SS-EN 6330 (domestic washing and drying procedures for textile testing), at 40°C using an eco-labelled washing powder for coloured garments. No subsequent tumble-drying was employed.

For those products in which the plain fabric was being investigated, any printed sections were removed from the product prior to washing in order to avoid any potential for different materials within printed sections contaminating the plain fabric with NPEs during the washing process.

Following a single wash, the fabric was dried and then a section of the fabric was isolated from the product and the concentration of NPEs was determined using an identical method to that described in Part 1.

Interspersed within the run of washes, two blank samples (plain fabric containing <1 mg/kg NPEs) were washed and subsequently analysed for their NPE content, in order to verify that the washing process did not result in contamination of samples.

Results and discussion

Table 6 presents the concentration of NPEs in sections of unwashed fabric and washed fabric for each product. The results for the unwashed fabric samples were determined for a portion isolated from each product without any other treatment (as presented in Part 1). Subsequently, the concentration of NPEs in washed fabric was determined in a separate portion isolated from the product after a single wash. For each product, the comparison between concentrations in washed and unwashed fabric is based upon total NPE concentrations determined for these two separate sections isolated from a single item.


Table 6. Concentrations of NPEs in washed fabric samples, and comparison with concentrations determined in a portion of unwashed fabric from the same product (as presented in Section 1). Limit of quantification = 1 mg/kg.

NPE concentration (mg/kg)

Sample code

Manufacturing brand

Unw

ash

ed

Wash

ed

NP

E c

onc.

in

wash

ed

sam

ple

as

% o

f co

nc.

in

unw

ash

ed

Fra

ctio

n o

f N

PE

ap

pare

ntly

w

ash

ed

out

(%)*

Kind of product

Fabric Country of purchase

Country of manufacture

Plain fabric samples

TX11061 G-Star RAW 11 9.1 83 17 Underwear 95% cotton 5% elastane

Netherlands China

TX11003 Adidas 18 1.8 10 90 Polo shirt 100% polyester

Thailand Thailand

TX11069 H&M 19 1.2 6 94 Polo shirt 100% cotton China China

TX11036** Converse 30 13 43 57 Sneakers Unknown Spain Vietnam

TX11074 Abercrombie & Fitch

39 4.6 12 88 T-shirt 100% cotton Denmark China

TX11014 Puma 47 26 55 45 Football shirt Unknown Switzerland Turkey

TX11049 Calvin Klein 160 25 16 84 Pyjama trousers

100% cotton Switzerland Sri Lanka

TX11046 Ralph Lauren 220 14 6 94 T-shirt 100% cotton Italy Philippines

TX11039 Youngor 530 240 45 55 Polo shirt Unknown China China

TX11019 Li Ning 680 380 56 44 Sport shirt Unknown Germany China

TX11028 Nike 810 100 12 88 T-shirt 58% cotton 42% polyester

Russia China

TX11073 Abercrombie & Fitch

1100 350 32 68 Jeans shorts 98% cotton 2% elastane

Japan China

Plastisol printed samples

TX11032 Converse 27000 12000 44 56 T-shirt Unknown Philippines Philippines

TX11051 Kappa 470 430 91 9 T-shirt Unknown Thailand Thailand

* Based on the assumption that the unwashed and washed portions from each item initially contained the same concentration of NPEs. Quoted values are the differences between concentrations in the washed and unwashed portions of each item, as a percentage of the concentration in the unwashed portion. ** Only the fabric portion of the sneaker was washed.

For all products investigated, the NPE concentrations in a washed portion were lower than concentrations in an unwashed portion of the same item, substantially lower in the majority cases.

For the plain fabric samples, the NPE concentrations in the washed portion were between 6% and 83% of the concentrations in the unwashed portion of the same product, with a median value of 24%. For all but one sample (TX11061), the washed portion concentration was less than 60% of the concentration for the corresponding unwashed portion, and for half the samples it was below 20% of the unwashed concentration.

Figure 1. Concentrations of NPEs in washed fabric (as % of concentration in unwashed fabric), for products with different levels of NPE in the unwashed products


The product with the smallest difference between levels in the washed and unwashed portions (TX11061, in which the washed portion contained NPEs at 83% of the level in unwashed portion) was also the product with the lowest initial level of NPEs (11 mg /kg NPEs in unwashed fabric). However, for two other items with NPE concentrations in unwashed fabric of below 20 mg/kg (TX11003 & TX11069), the level of NPEs in the washed portions was 10% or less of that in the respective unwashed portion. These results suggests that the smaller difference between levels of NPEs in washed and unwashed fabric for TX11061 was not due to the low level of NPEs in this product.

Indeed, for the plain fabric samples as a whole, the washed portion concentration (as a percentage of the unwashed value) was largely independent of the level of NPEs in the product. See Figure 1.

Though the data are limited, the results from this study suggest that the type of fabric that a product is made from is not a significant factor influencing the extent to which concentrations are lower in the washed portion compared to the unwashed portion. Values of 10% or less were found for one or more products composed of either 100% cotton or 100% polyester.

For the two plastisol printed samples, the results show a considerable difference between the effects of washing on the two samples. For the sample with the highest concentration of NPEs in the unwashed portion (TX11032, 27000 mg/kg), the concentration in the washed portion was 44% of this value. The sample with the lower concentration in the unwashed sample (TX11051, 470 mg/kg) gave a far smaller difference between the values for the washed and unwashed portions, with the concentration in the washed portion being 91% of that in the unwashed portion.

Conclusions

This study has demonstrated the widespread presence of NPEs within textile products, across almost all countries of manufacture, countries of purchase and brands included in the study, indicating that the use of NPEs is widespread within the international textile industry, including within supply chains used by several major international clothing brands.

The presence of NPE residues in a finished product available on the market strongly indicates their use during the manufacture of the product, but does not give information regarding the amount of NPEs used during its manufacture as residue levels will inevitably depend on a range of other factors, including the number and efficacy of wash cycles employed during product finishing. If NPEs are more efficiently washed out from materials during manufacture and finishing, this will inevitably result in a lower level of NPE residues in the final product, but at the same time would represent an increase in the quantities of NPEs released to water at source (in the country of manufacture). In the context of the current study, a finished article found to contain a low level of NPEs might nonetheless have been manufactured using higher quantities of NPEs than one found to contain higher residue concentrations, but with more of the NPEs being washed out before the product came to market. It also follows that, where NPEs were not identified for an individual item, the result does not demonstrate that the item was manufactured without the use of NPEs.

Information concerning the country of manufacture and sale, type of product and fabric and brand are provided for completeness and transparency, and should not be taken to imply that the results obtained are therefore representative of residue levels which may be expected for all such products within those categories. Rather, this study provides a snapshot of what appears to be a more generic problem that is not restricted to any particular country, product type or brand, and one that deserves further investigation including from a regulatory perspective.

The possible presence of residues of other hazardous substances deriving from product manufacture was not investigated in this study

Analysis of washed samples

Assuming that the unwashed portion and the washed portion from each item initially contained the same concentration of NPEs, these results indicate that a single wash – using conditions intended to simulate standard domestic laundering – can wash out a substantial fraction of NPE residues present within textile products. For 11 of the 12 plain fabric samples tested in this way, the concentration of NPEs in washed fabric was less than 60% of the concentration found in unwashed fabric, and in half of the 12 samples the amount was less than 20%.

Therefore, using the same assumption, the results equate to between 17% and 94% of NPE residues being washed out from the fabric during a single wash, with more than 80% being washed out for half the samples.

Though limited in scope compared to the broad range of textile products on the market, the results also indicate that the extent to which NPEs are washed out under such conditions is largely independent of the initial level of NPE in the


unwashed product, and of the type of fabric that a product is made from. However, more extensive analysis of a wider range of products would be required in order to confirm the lack of such relationships.

In addition to the plain fabric samples, two samples of fabric that included a plastisol print were also investigated. The results demonstrate that it is possible for there to be a similar reduction in the concentration of NPEs in plastisol printed fabric following a single wash compared to plain fabrics. However, the results for one of the two plastisol printed samples indicate that NPE residues within plastisol printed fabrics may be less readily washed from an item in some cases.

As NPEs are readily water-soluble compounds, it can therefore be expected that they can be readily released from fabrics under standard washing conditions. However, as far as we are aware, this study is the first to report differences in the amounts of NPEs in fabric products before and after washing using simulated domestic laundering conditions.

It has previously been reported that NPEs can be detected in wash water following the washing of textile products under simulated domestic laundry conditions, though the amounts of NPEs in the wash water as a fraction of the total quantity of NPEs in the fabric prior to washing were not determined (Larsen et al. 2000).

Although the level of NPEs in any given article of clothing is relatively small, the sheer volume of clothing being sold and subsequently washed means that the total quantities of NPEs being released may be substantial.

Nonylphenol, formed from the partial breakdown of NPEs, continues to be detected in many rivers within the EU, often in relatively high concentrations compared to levels of other organic chemical pollutants monitored (EA 2011, Greenpeace 2010). Furthermore, monitoring data shows ongoing substantial releases of nonylphenol to surface waters within the EU, predominantly via urban wastewater and sewage treatment plants. Data, primarily that published through national and EU pollutant release and transfer registers (PRTRs), is relatively detailed for some EU member states, though few or no data are available for others (Greenpeace 2010).

It has been estimated that residues of NPEs and nonylphenol present in textile and leather goods in parts of Sweden were by far the most significant source of these chemicals entering wastewater treatment facilities in 2004, accounting for many tonnes a year. These calculations demonstrate the potential cumulative impact arising from the presence of relatively low concentrations of these chemicals in individual textile products (Månsson et al. 2008).

Despite requirements made in 2000 under the Water Framework Directive (WFD) that all emissions, discharges and losses of ‘priority hazardous substances’ be phased out within 20 years, which includes nonylphenol (EU 2001), inputs of nonylphenol to surface waters are ongoing within the EU.

Controls on the marketing and use of nonylphenol and NPEs have been in place within the EU since 2005, under which products containing greater than 0.1% of nonylphenol or NPEs may no longer be placed on the market, with some minor exceptions principally for closed loop industrial systems (EU 2003). However, restrictions on the import of textile products containing residues of NPEs from outside the EU have yet to be developed.

When restrictions on NPE residues in imported products are introduced, a maximum allowed limit of 100 mg/kg (0.01%) would fail to offer adequate protection, as the results from this study have demonstrated. Only 14 of the 52 products that tested positive for NPEs contained concentrations above 100 mg/kg, and yet the cumulative release of NPEs from products imported into the EU that contained levels of NPEs in a similar range to that found in this study would be considerable.

Therefore, a substantially lower limit than 100 mg/kg (0.01%) would need to be applied to offer adequate protection of European surface waters against inputs of NPEs and NP. Achieving this would require employing the lowest achievable level for verifying the presence of NPE residues in such products.

The Swedish government has recently submitted notifications of intention to propose restrictions on the sale of textile and leather articles containing residues of nonylphenol or NPEs within the EU (ECHA 2011). However, until adequate measures become effective, releases of NPEs from textiles and the resulting inputs of nonylphenol to surface waters within the EU will continue.

Similarly, in countries outside the EU, releases of NPEs and nonylphenol to surface waters will continue until measures are in place that prevent their manufacture, use and release, including as a result of the import of products containing residues of these substances. Such measures would include legislation, in conjunction with changes in company/ brand policies, requiring the elimination of all uses and releases from their supply chains and their products.


References

Brigden K, Allsopp M & Santillo D (2010). Swimming in Chemicals: Perfluorinated chemicals, alkylphenols and metals in fish from the upper, middle and lower sections of the Yangtze River, China. Greenpeace Research Laboratories Technical Note 07/2010. http://www.greenpeace.to/publications/swimming-in-chemicals.pdf

ECHA (2011). Registry of intentions for Annex XV dossiers. Notification of intention to propose restriction on the placing of the market of textile and leather articles containing nonylphenol (NP) or nonylphenol ethoxylates (NPEO), submitted by Sweden on 02-09-2001 to the European Chemicals Agency (ECHA). http://echa.europa.eu/web/guest/registry-of-current-restriction-proposal-intentions

EEA (2011). Hazardous substances in Europe’s fresh and marine waters - An overview. Technical report No 8/2011, European Environment Agency (EEA), Copenhagen, Denmark. http://www.eea.europa.eu/publications/hazardous-substances-in-europes-fresh

EU (2001). Decision No 2455/2001/EC of the European Parliament and of the Council of 20 November 2001 Establishing the List of Priority Substances in the Field of Water Policy and Amending Directive 2000/60/EC, Official Journal L 249 , 17/09/2002: 27-30

EU (2003). Directive 2003/53/EC of the European Parliament and of the Council of 18 June 2003, amending for the 26th time Council Directive 76/769/EEC relating to restrictions on the marketing and use of certain dangerous substances and preparations (nonylphenol, nonylphenol ethoxylate and cement), now entry number 46 of annex 17 of Commission Regulation (EC) No 552/2009 of 22 June 2009 amending Regulation (EC) No 1907/2006 of the European Parliament and of the Council on the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) as regards Annex XVII. Official Journal L 164. 26.6.2009: 7-31

Greenpeace (2004). Finding Chemo - Toxic Childrenswear by Disney. http://www.greenpeace.org/international/en/publications/reports/finding-chemo-toxic-children/

Greenpeace (2010). Heads in the sand over Europe's most dangerous chemicals: governments ignoring legal obligations in the phasing out of nonylphenol water pollution. http://www.greenpeace.org/eu-unit/en/Publications/2010/NP-pollution-12-05-10/

Greenpeace (2011a). Dirty Laundry. Unravelling the corporate connections to toxic water pollution in China, including the Technical note. http://www.greenpeace.org/dirtylaundryreport

Greenpeace (2011b). Dirty Laundry 2: Hung Out to Dry. Unravelling the toxic trail from pipes to products. http://www.greenpeace.org/international/en/publications/reports/Dirty-Laundry-2/

Jobling S, Sheahan D, Osborne JA, Matthiessen P & Sumpter JP (1996). Inhibition of testicular growth in rainbow trout (Oncorhynchus mykiss) exposed to estrogenic alkylphenolic chemicals. Environmental Toxicology and Chemistry 15(2): 194-202

Larsen FH, Helweg C, Pedersen AR, Boyd HB, Lauresen SE & Hansen J (2000). Chemicals in Textiles, Environmental Project 534 - 2000. Commissioned by the Danish Environmental Protection Agency. http://www.statensnet.dk/pligtarkiv/fremvis.pl?vaerkid=6585&reprid=0&filid=34&iarkiv=1

Laursen SE, Hansen J, Drøjdahl A, Hansen OC, Pommer K, Pedersen E & Bernth N (2003). Survey of chemical compounds in textile fabrics. Survey no. 23, on behalf of the Danish Environmental Protection Agency. http://www.mst.dk/NR/rdonlyres/B9CDE217-9E41-4F27-A8A3-921D5B50A737/0/23.pdf

LGC (2006). Determination of specific alkylphenol ethoxylates in textiles, Government Chemist Programme, LGC. http://www.governmentchemist.org.uk/dm_documents/Determination%20of%20specific%20alkylphenol%20ethoxylates%20in%20textiles_6sQz8.pdf

Månsson N, Sörme L, Wahlberg C & Bergbäck B (2008). Sources of Alkylphenols and Alkylphenol Ethoxylates in Wastewater—A Substance Flow Analysis in Stockholm, Sweden. Water Air Soil Pollution: Focus 8: 445–456

OSPAR (2004). Nonylphenol/nonylphenolethoxylates, OSPAR Priority Substances Series 2001, updated 2004, OSPAR Convention for the Protection of the Marine Environment of the North-East Atlantic, OSPAR Commission, London, ISBN 0-946956-79-0: 20 pp.

SSNC (2008). T-shirts with a murky past, Swedish Society for Nature Conservation (SSNC). http://www.naturskyddsforeningen.se/upload/report-t-shirts-with-a-murky-past.pdf

Ap

pe

nd

ix 1

Table A1.1. Concentrations of NPEs in individual articles, by country of purchase and by brand

Country of purchase NPE concentration (mg/kg) Sample code Brand 29 TX11050 Calvin Klein

2.0 TX11027 Nike

1.2 TX11015 Puma

Argentina (4 of 4)

51 TX11045 Ralph Lauren <1 TX11009 Adidas

<1 TX11042 H&M

970 TX11054 Kappa

Austria (2 of 4)

12 TX11030 Nike <1 TX11001* Adidas

<1 TX11047 Calvin Klein

19 TX11069 H&M

9.8 TX11018 Li Ning

<1 TX11022* Nike

210 TX11010 Puma

2.2 TX11065 Uniqlo

530 TX11039 Youngor

190 TX11037 Youngor

China (7 of 10)

19 TX11069 Youngor <1 TX11052 Kappa

<1 TX11058 Lacoste

<1 TX11025 Nike

Czech Republic (1 of 4)

1.8 TX11006 Puma 39 TX11074 Abercrombie & Fitch

<1 TX11034 Converse Denmark (2 of 3)

35 TX11043 Ralph Lauren Finland (1 of 1) 660 TX11024 Nike

<1 TX11002 Adidas

140 TX11031 Converse

<1 TX11060 G-Star RAW

24 TX11055 Kappa

680 TX11019 Li Ning

<1 TX11076 Nike

Germany (4 of 7)

14 TX11011 Puma 2.0 TX11008 Adidas

240 TX11053 Kappa

<1 TX11029 Nike

Italy (3 of 4)

220 TX11046 Ralph Lauren 1100 TX11073 Abercrombie & Fitch

9.1 TX11048 Calvin Klein

<1 TX11040 Gap

<1 TX11023 Nike

Japan (3 of 5)

8.7 TX11066 Uniqlo <1 TX11004 Adidas

1.6 TX11033 Converse

11 TX11061 G-Star RAW

<1 TX11062 G-Star RAW

Netherlands (3 of 5)

21 TX11070 H&M 14 TX11005 Adidas Norway

(2 of 2) 13 TX11063 G-Star RAW 27000 TX11032* Converse

<1 TX11057 Lacoste

7.1 TX11021 Li Ning

Philippines (2 of 4)

<1 TX11012 Puma 5.0 TX11072* H&M

810 TX11028 Nike

4.4 TX11017 Puma

Russia (4 of 4)

25 TX11068 Uniqlo 30 TX11036 Converse

41 TX11064* G-Star RAW

<1 TX11059 Lacoste

Spain (3 of 4)

12 TX11016 Puma <1 TX11071 H&M Sweden

(0 of 2) <1 TX11013* Puma 1.1 TX11077 Adidas

160 TX11049 Calvin Klein

3.1 TX11078 H&M

1.2 TX11026 Nike

47 TX11014 Puma

Switzerland (5 of 6)

<1 TX11044 Ralph Lauren 18 TX11003 Adidas

470 TX11051* Kappa

3.6 TX11056 Lacoste

Thailand (4 of 4)

2.8 TX11020 Li Ning 18 TX11075 Abercrombie & Fitch

<1 TX11007 Adidas

17 TX11035 Converse

<1 TX11041 Gap

UK (2 of 5)

<1 TX11067 Uniqlo

* Indicates analysis of a section of fabric bearing a plastisol print

Table A1.2. Concentrations of NPEs in individual articles, by country of manufacture and by brand

Country of manufacture NPE conc (mg/kg) Sample code Brand 41 TX11064*

13 TX11063

<1 TX11060

G-Star RAW

21 TX11070

3.1 TX11078

<1 TX11042

<1 TX11071

H&M

970 TX11054 Kappa

4.4 TX11017 Puma

51 TX11045 Ralph Lauren

Bangladesh (8 of 11)

25 TX11068 Uniqlo 18 TX11075 Abercrombie & Fitch Cambodia

(2 of 2) 1.2 TX11026 Nike 1100 TX11073

39 TX11074 Abercrombie & Fitch

14 TX11005

<1 TX11009

<1 TX11001*

<1 TX11002

<1 TX11007

Adidas

<1 TX11047 Calvin Klein

17 TX11035 Converse

<1 TX11040 Gap

11 TX11061 G-Star RAW

19 TX11069 H&M

24 TX11055 Kappa

680 TX11019

9.8 TX11018

7.1 TX11021

Li Ning

810 TX11028

660 TX11024

<1 TX11022*

<1 TX11029

Nike

210 TX11010

1.2 TX11015 Puma

<1 TX11044 Ralph Lauren

8.7 TX11066

2.2 TX11065 Uniqlo

530 TX11039

190 TX11037

China (19 of 28)

19 TX11038

Youngor

Egypt (1 of 1) 9.1 TX11048 Calvin Klein 2.0 TX11027 Nike

<1 TX11012 Puma Indonesia (2 of 3)

35 TX11043 Ralph Lauren 2.8 TX11020 Li Ning Malaysia

(2 of 2) 12 TX11016 Puma Pakistan (1 of 1) 240 TX11053 Kappa

1.1 TX11077

<1 TX11004 Adidas

27000 TX11032* Converse

Philippines (3 of 4)

220 TX11046 Ralph Lauren Sri Lanka (1 of 1) 160 TX11049 Calvin Klein

18 TX11003

2.0 TX11008 Adidas

29 TX11050 Calvin Klein

470 TX11051* Kappa

3.6 TX11056 Lacoste

Thailand (5 of 6)

<1 TX11023 Nike Tunisia (0 of 1) <1 TX11062 G-Star RAW

1.6 TX11033

<1 TX11034 Converse

5.0 TX11072* H&M

12 TX11030

<1 TX11025

<1 TX11076

Nike

47 TX11014

1.8 TX11006

Turkey (5 of 9)

<1 TX11013*

Puma

140 TX11031 Converse

30 TX11036

<1 TX11041 Gap

<1 TX11052 Kappa

14 TX11011 Puma

Vietnam (3 of 6)

<1 TX11067 Uniqlo <1 TX11057

<1 TX11058 Unknown (3 of 3)

<1 TX11059

Lacoste

* Indicates analysis of a section of fabric bearing a plastisol print

Table A1.3. Concentrations of NPEs in individual articles by brand, with the kind of product and fabric where known

Brand NPE conc. (mg/kg) Sample code Country of purchase Country of manufacture Kind of product Fabric 1100 TX11073 Japan China Jeans shorts Cotton + 2% elastane

39 TX11074 Denmark China T-shirt Cotton Abercrombie & Fitch

18 TX11075 UK Cambodia T-shirt Cotton 18 TX11003 Thailand Thailand Polo shirt Polyester

14 TX11005 Norway China Dress Cotton

2.0 TX11008 Italy Thailand Football shirt Polyester

1.1 TX11077 Switzerland Philippines Tracksuit trousers -

<1 TX11001* China China T-shirt -

<1 TX11002 Germany China Football shirt Polyester

<1 TX11004 Netherlands Philippines Tracksuit jacket -

<1 TX11007 UK China Sweatshirt -

Adidas

<1 TX11009 Austria China Tracksuit trousers - 160 TX11049 Switzerland Sri Lanka Pyjama trousers Cotton

29 TX11050 Argentina Thailand Underwear Cotton + 5% elastane 9.1 TX11048 Japan Egypt Underwear Nylon + 28% elastane

Calvin Klein

<1 TX11047 China China Underwear Cotton 27000 TX11032* Philippines Philippines T-shirt -

140 TX11031 Germany Vietnam Sneakers -

30 TX11036 Spain Vietnam Sneakers -

17 TX11035 UK China Sneakers -

1.6 TX11033 Netherlands Turkey T-shirt Cotton

Converse

<1 TX11034 Denmark Turkey T-shirt Cotton 41 TX11064* Spain Bangladesh T-shirt Cotton 13 TX11063 Norway Bangladesh T-shirt Cotton

11 TX11061 Netherlands China Underwear Cotton + 5% elastane <1 TX11060 Germany Bangladesh T-shirt Cotton

G-Star RAW

<1 TX11062 Netherlands Tunisia Jeans Cotton <1 TX11040 Japan China T-shirt Cotton

Gap <1 TX11041 UK Vietnam T-shirt Cotton 21 TX11070 Netherlands Bangladesh Tank top Cotton 19 TX11069 China China Polo shirt Cotton

5.0 TX11072* Russia Turkey T-shirt Cotton + 13% viscose 3.1 TX11078 Switzerland Bangladesh Shirt Cotton <1 TX11042 Austria Bangladesh T-shirt Cotton

H&M

<1 TX11071 Sweden Bangladesh Sweatshirt Cotton 970 TX11054 Austria Bangladesh T-shirt Cotton

470 TX11051* Thailand Thailand T-shirt -

240 TX11053 Italy Pakistan Tracksuit Polyester

24 TX11055 Germany China Football shirt Polyester

Kappa

<1 TX11052 Czech Republic Vietnam Sweatshirt - 3.6 TX11056 Thailand Thailand Polo shirt Cotton + 6% elastane

<1 TX11057 Philippines unknown Polo shirt Cotton

<1 TX11058 Czech Republic unknown Polo shirt Cotton

Lacoste

<1 TX11059 Spain unknown Polo shirt Cotton 680 TX11019 Germany China Sport shirt -

9.8 TX11018 China China Polo shirt 54% Cotton + 46% polyester

7.1 TX11021 Philippines China T-shirt Polyester

Li Ning

2.8 TX11020 Thailand Malaysia Polo shirt Polyester + 12% elastane 810 TX11028 Russia China T-shirt 58% Cotton + 42% polyester

660 TX11024 Finland China T-shirt 58% Cotton + 42% polyester

12 TX11030 Austria Turkey T-shirt Cotton

2.0 TX11027 Argentina Indonesia Tracksuit jacket 65% cotton, 31% polyester, 4% elastane

1.2 TX11026 Switzerland Cambodia Polo shirt Polyester + 12% elastane

<1 TX11022* China China T-shirt -

<1 TX11023 Japan Thailand Sport shirt Polyester

<1 TX11025 Czech Turkey T-shirt Polyester

<1 TX11029 Italy China T-shirt Cotton

Nike

<1 TX11076 Germany Turkey Tank top Cotton 210 TX11010 China China T-shirt -

47 TX11014 Switzerland Turkey Football shirt -

14 TX11011 Germany Vietnam Sport shorts Polyester

12 TX11016 Spain Malaysia Tracksuit jacket Polyester

4.4 TX11017 Russia Bangladesh T-shirt -

1.8 TX11006 Czech Turkey Football shirt 80% Cotton + 20% polyester

1.2 TX11015 Argentina China T-shirt Cotton

<1 TX11012 Philippines Indonesia Sport shirt Polyester + 9% elastane

Puma

<1 TX11013* Sweden Turkey T-shirt - 220 TX11046 Italy Philippines T-shirt Cotton

51 TX11045 Argentina Bangladesh Jeans Cotton

35 TX11043 Denmark Indonesia Polo shirt Cotton

Ralph Lauren

<1 TX11044 Switzerland China Polo shirt Cotton 25 TX11068 Russia Bangladesh Jeans Cotton

8.7 TX11066 Japan China Polo shirt 65% cotton, 30% polyester,

5% elastane

2.2 TX11065 China China T-shirt -

Uniqlo

<1 TX11067 UK Vietnam Jeans Cotton + 2% elastane 530 TX11039 China China Polo shirt -

190 TX11037 China China Polo shirt -

Youngor

19 TX11038 China China Shirt - * Indicates analysis of a section of fabric bearing a plastisol print

Documents

Nonylphenol ethoxylates (NPEs) in textile products, and their